Resinous compositions of styrene, castor oil, and a diisocyanate



l atented Sept. 2, 1952 RESINOUS COMPOSITIONS OF STY RE NE, CASTOR OIL, AND A DIISOCYANATE William E. Cass, Schenectady, N. Y., assignor to General Electric Company, a corporation of New York No Drawing. Application February 4, 1950, Serial No. 142,539

This invention is concerned with resinous compositions comprising castor oil, an organic diisocyanate, and styrene. More particularly, the invention relates to a composition of matter comprising (a) styrene, (b) castor oil, both in the hydrogenated and raw unhydrogenated form, and (c) an organic compound containing two -NCO groups. The invention embraces both liquid, soluble, fusible products as well as solid, nonfusible, insoluble compositions prepared from the soluble, fusible materials. For purposes of brevity, the term castor oilwill be used hereinafter in the specification and in the appended claims to designate both the hydrogenated and unhydrogenatedforms.

U. S. 2,358,475, issued September 19, 1944, discloses varnishes comprising modified drying oils 7 obtained by reacting the oils with a diisocyanate. This patent also includes disclosures that various synthetic resins such as polystyrene, polyvinyl chloride, etc., may be added after the diisocyanate modifier has reacted with the oils in question. Mylinvention differs from that disclosed in the aforementioned patent in that instead of using syntheticresins with the varnishes obtained from the 1 drying oils and the isocyanates, I employ monomeric styrene ratherthan polymeric styrene. In addition, I do not precondense the styrenewith the drying oil prior to modification with thediisocyanate, but rather interact the castor oil with the diisocyanate in the presence of the styrene. This latter distinction is an important one since my invention yields entirely different products than thoseobtained when the styrene is intercondensed with the drying oil and thereafter modified with a diisocyanate in accordancewith the teachings of the aforementioned patent. The products obtained in accordance with my inventionhave unique properties which make them suitable for such applications as molding,

casting, and laminating in the plastics field. Un-

expectedly, it was found that of all the monomeric materials available, only styrene was able togive these unique, highly desirable properties. It was found that when other monomeric materials such as, for instance, methyl methacrylate, vinyl acetate, diallyl phthalate, etc., were employed in place of the styrene, the resulting compositions when cured to the substantially iniusible, insoluble form were cheesy weak gels, which was in strong. contrast to the properties of the styrene-modified materials which were strong, insoluble, tough materials.

- .Inaccordance with one of the embodiments of myinvention, castor oil and a diisocyanate (for example, one corresponding to a, general formula QCN,R -NCO, where R is a divalent organic radical, for example, alkylene, arylene, alkaryleneparalkylene, etc., as'well asother or similar divalent organic radicals containing substituents 24 Claims. (Cl. 260-23) thereon which are non-reactive with the diisocyanate, styrene, or castor oil) are mixed together in the proper proportions and heated to obtain a soluble resin. This resin can be dissolved in monomeric styrene to form a varnish. Alter.- natively, all three ingredients may be mixed simultaneously and the heating omitted, to form a varnish. In many cases heating of the castor. oil-diisocyanate mixture is not necessary since the mere addition of thediisocyanate'results in an exothermic reaction which may cause linking of the castor oil molecules; Thereafter in many applications, additional diisocyanate (in anamount necessary toelfect cross-linking, of the resin) as well as a vinyl polymerization catalystfor the styrene may be added to the aforementioned varnish and this latter mixture preferably: heated until a solid,.infusible, tough materialis obtained. Prior to the latter heat treatment, the mixture of ingredients may be cast in various molds or may be employed to impregnate various fillers such as glass fibers, asbestos fibers, titanium dioxide, cellulosic fillers (such as wood flour), cloth cuttings, etc., and this mixture molded under heat and pressure to give useful objects; Alternatively, the varnish with the additional amount of diisocyanate and the vinyl polymerization catalyst may be employed to coat and im-. pregnate various sheet materials used in the laminating art, the impregnated sheets superposed upon each other and molded under heat" and pressure to give useful laminated panels.-

In preparing the initial-varnish comprising the styrene, the castor oil, and the diisocyanate, the ratio of ingredients employed in this mixture may be varied depending upon the properties desired: in the final product. In general, the-sts'rer e ispreferably' present in an amount ranging from l to 99% of the total weight of the three ingre:

dients. Preferably the styrene comprises from v 10 to by weight, of the total weight of the castor oil, styrene and diisocyanate. The amount of castor oil and. diisocyanate employed may also be varied without-departingfrom the scope of the invention. Thus thecasterv oil may comprise from 5 to of the total weight of the three ingredients, preferably from 25 to 75% ofthetotal weight of the styrene,;; castor, oil, and diisocyanate. In generaLthe use of increasingly larger amounts of styrene inthe reaction mixture tends to giveharder and less consider the particular diisocyanate employed aisl; well as the type of product desired. Generally,

the diisocyanate is advantageously present in a molar ratio ranging up to 2 mols of the diisocyanateper mol of the castoroil.

of diisocyanate" castor oil, e. g., from 0.1 to 1 mol of the di-I isocyanate per mol of the castor oil. To obtain insoluble, infusible products it is advisable that the diisocyanate be present in a molar ratio equal to more than 1 but less than 2 mols of the diisocyanate per mol of castor oil in the mixture of ingredients; the preferred range in such a case being about 1.01-1 .5 mols of the diisocyanate per mol castor oil. It will of course be apparent to those skilled in the art that smaller or larger ratios of diisocyanate and castor oil may be employed without departing from thel'scope of. the invention. In general, the molar ratios used in a particular instance will depend -.upon such factors, as for example, the kind of diisocyanate employed, whether thehydrog'enated or non-hydrogenated castor oil is used, the properties desired, etc. It has been found in-many applications that the usual preferred ratio is slightly more than 1 mol of the diisocyanate per mol of the castor oil in order to obtain soft products, and above 1 up to and includinglfi molsuof the diisocyanate per mol of the castor oil toobtain firmer products The use of more than 2 mols diisocyanate per mol castor oil yields again fusible, soluble products andinorder to obtain, solid, infusible, insoluble productsadditional amounts of castor oil are required.

In calculating themolar ratio of diisocyanate to castor oil it will be apparent that the molecular and equivalent weight of the castor oil should be taken into consideration. As is known, castor oil comprises essentially glycerol triricinoleate. If castor oil were the glycerol ester entirely, its molecular weight would be 932 and its equivalent weight 311 (hydroxyl basis). However,- castor oil because of the presence of smalleramounts of other fatty materials has an average acetyl value of 148. This latter average corresponds to an equivalent weight of 3'79 (on hydroxylbasis) or an apparent molecular weight of 1135. It is this latter value of 1135- which has been used in the succeeding examples for calculating ratios of castor oil to diisocyanates in-making the various varnishes or solid prodnets with styrene. For many purposes, on a weight basis, good results are obtained when thediisocyanate comprises from 1 to based onthe'weight of the castor oil in order to obtain liquid, fusible products and from 15 to 30 of th'e diisocyanate based on the weight of the castor'oil in order to obtain solid, infusible, in-

soluble products. In the case of hexamethylenediisocyanate, I have found it advantageous to use from 15 to 23%, by weight, of the latter based on the weight of the castor oil.

iii-making the varnishes from styrene, castor oil and the diisocyanate, it is desirable and in many instances essential that no vinyl polymerization catalyst be employed at the start. However, in order to obtain the tough, solid products described above, it is essential that after preparation of the varnish from the styrene, castor oil and diisocyanate, there be added a vinyl polymerization catalyst together with an addi tional amount of diisocyanate which may be necessary to complete conversion of the liquid product to the solid, infusible, insoluble state. The amount of vinyl polymerization catalyst employed may, of course, be varied within wide limits, for example, from 0.01 to 4.0% byweight or higher, preferably from.-0. 1 to 2.0% by weight,

based on the weight of the styrene. It will of course be understood that any one or more of 'the well-known vinyl polymerization catalysts tained when benzoyl peroxide suitable for effecting polymerization of the styrene may be employed. Among these may be mentioned, for example, benzoyl peroxide, diacetyl peroxide, benzoyl acetyl peroxide, tertiary butyl peroxide, tertiary butyl hydroperoxide-l, ditertiary *butyl 'perphthalate, 2-azo-bis-isobutyronitrile etc. Good results have been obis employed as the vinyl polymerization catalyst although it is to be understood that any other well-known vinyl polymerization catalyst may be employed without departing from the scope of the invention.

As pointed out previously, the diisocyanates employed in the practice of the instant invention are those corresponding to the general formula OCNR-NCO, where R has the meaning given above. Among such diisocyanates may be mentioned ethylene diisocyanate, decamethylene diisocyanate, hexamethylene diisocyanate, propylene, 1,2-diisocyanate, tetramethylene diisoc'yanate, butylene 1,3-diisocyanate, ethylidene diisocyanate, cyclopentylene 1,3-diisocyanate, cyclohexylene 1,3-diisocyanate, 1-methylphenylene 2,4-diisocyanate, diphenyl 4,4"-diisocyanate, .pisocyanato benzyl isoicyanate, etc. Other diisocyanates containing substituents which are essentially inert to any of the reactants'in the mixture of ingredients may be employed without departing from the scope of the invention. Ifdesired, corresponding diisothiocyanates may also be used.

In preparing the varnishes coming withinthe scope of my invention, one method comprises mixing the castor oil and the diisocyanat'e, the latter being present in an amount insuflioient to effect gelation of the castor oil, and the mixture preferably heated at a temperaturerangingfrom slightly above room temperature to around C., for example, from 40-l'00 C. Although reaction may take place at room temperature due to the exothermic characteristic of the reaction, nevertheless, for many pratical purposes sheep-- plication of heat is desirable. Thereafter, the styrene, preferably at room temperature, is -incorporated with the resin to form a varnish. If it is desired to obtain solid, infusible, insoluble materials, the varnish or liquid, soluble composition described immediately preceding is .then mixed with an adequate amount of vinyl 'polymerization catalyst for the styrene and Withan additional amount of a diisocyanate sufiicientto cause cross-linking of the'castor oil. The castor oil, used is preferably substantially free of water and may. comprise raw castor oil or' hydrogenated castor oil.

Another method for making the claimed com-- positions of matter coming within the scope of Heating of this mixture at temperatures above room temperature accelerates the conversion of this mixture .tothe solid, tough, flexible, infusible, insoluble state.

It has been found advantageous in instanceswhere the styrene, castor oil, d-iisocyanate and vinyl polymerization catalyst were intended to be converted in situ to the solid, infusible, iii-- soluble state, as for instance, in casting applications, to degas the mixture, 1. e to remove any trapped air, or any liberated carbon dioxide, .by placing the mixture of ingredients under a vacuum for a period of time ranging, for instance, from about to 30 minutes after mixing while preferably agitating the mixture. By this simple process, it is possible to obtain clear bubble-free converted products.

In order that those skilled in the art may better understand how the present invention may be practiced, the following examples are given by way of illustration and not by way of limitation. All parts are by weight.

Example 1 About 93 parts non-hydrogenated castor oil and 22 parts hexamethylene diisocyanate, were mixed together and degassed. To the resulting solution was added 50 parts monomeric styrene containing 1%, by weight, benzoyl peroxide. The

In this example, two additional samples were prepared in which the same ingredients were employed as in Example 1 except that in one sample 100 parts styrene and in the other sample 150 parts styrene, each containing 1%, by weight, benzoyl peroxide, were substituted for the'50 parts of styrene employed in the aforementioned Example 1. The mixtures were heated in the same manner to yield polymers Whose hardness and toughness increased with the increasing styrene content.

Example 3 In this example 93 parts non-hydrogenated castor oil and 23 parts toluene diisocyanalte were thoroughly mixed together and degassed. Thereafter 50 parts monomeric styrene, containing 1%, by weight, benzoyl peroxide, was added tothe mixture and this solution was heated for 24 hours at 80 C. and for an additional 24 hours at 100C. to obtain a polymer which was more translucent, harder and tougher than the polymers obtained in Examples 1 and 2 usinghexamethylene diisocyanate. y l

When methyl methacrylate (plu 1% benzoyl peroxide) in an equal amount was substituted for the styrene in the mixture of ingredients described in Example 3 and the solution heated about hours at 80 0., 4 hours at 100 C. and 2 hours at 125 0. there was obtained a weak gel which was much less toughv than wasv obtained in the case of monomeric styrene.

Example 4 This example illustrates the effect of using polystyrene in place of monomeric styrene with the above identified ingredients. More particularly, it was found that it was impossible to incorporate polystyrene in the castor oil-diiso-cyanate system without the use of a mutual solvent due to the insolu-bility of thepolystyrene in such a system. When a mutual solvent was employed, however, it had to be present in aconsiderable amount. Thus, when 20 parts non-hydrogenated castor oil was added to a solution of 5 parts polystyrene in 20pa1'ts benzene, most of the polystyrene precipitated. By using 5 parts ,p0lystyrene, 5 parts castor oil and 1.2 parts toluene diisocyana-te in 50 parts benzene, there was finally obtained a system which at least initially. appeared to be homogeneous. A sample of this solution was poured on a glass surface and also cast in a small beaker and each of the samples heated at a temperature of about C. ior18 hours. At the end of this time both the film sample on the gl assiplate and the cast sample were whitish resinous materials. However, physically they were much weaker and much less flexible than a castor oil-diisocyanate-styrene polymer prepared in essentially the same ratio of ingredients but omitting the polystyrene and instead using monomeric styrene plus a vinyl polymerization catalyst which wa disclosedabove in Example 3. The sample prepared with the polystyrene had such poor 'physical'prope'rties that it appeared useless for any practical application.

The attempt to use other polymerizable mono: mers in my system in place of styrene such as, for example, vinyl acetate, butyl methacrylate, ethyl acrylate and'diallyl phthalate resulted in products which also were very weak and cheesy and appeared to be practically useless. f The following example illustrates the preparation of stable, solventless varnishes which can be prepared by employingan amount of diisocyanate insufiicient to cause gelation ofthefmixture of ingredients. Subsequent addition of an organic diisocyanate and vinyl polymerization catalyst caused conversion of the ingredients to the insoluble, infusible state.

Example 5 In this example 16.8 parts hexamethylcne diisocyanate was mixed with 113.5 parts nonhydrogenated castor oil and heated at C, for 3 hours. The resulting composition was cooled, dissolved in an equal weight of monomeric styrene (containing quinone as a polymerization'inhibitor) and degassed. A varnish stable at room temperature for at least a month was obtained. When 0.5%, by weight, benzoyljperoxide and 2.6%, by weight,hexamethylene diisocyanate (each being based on the weight of the varnish). was added to the varnish and the resultant mixture heated for 2 hours at 80 C. and 16 hours at 100 C., a white, flexible, tough resin was obtained.

Similar products were obtained asin Example 5 when either 1.9% or 3.1% hexamethylene id'iisocyanate was substituted for the 2.6%,by weight, hexamethylene diisocyanate employed in Exam: ple 5 (using the same amount, 0.5%, by weight, benzoyl peroxide). At the lower concentration of hexamethylene diisocyanate, i. e., 1.9%, the product was softer and more flexible while at the higher concentration of the diisocyanate (3.1%) the product was harder and tougher than that obtained in Example 5. v p

When the polymer obtained in Example 5' above was subjected to temperatures ranging from 100- C. for extended periods ofv time, it was found that the toughness and rubbery and flexible prop; erties remained even at these temperatures. is; inp contrast itothe usual rilbberymolyesters castingresins *which tend to-"becoiiie cheesy as the teniperature is r'aised.

Q EatdmpZe-(z *Esmmple 7 Another stable varnishwas prepared-by formingga mixture otingredientscomprising 17.4.parts toluene diisocyanate and 1.13.5-parts non-hydrogenated castor oil and-heating this-mixtureior 3 hours; at 100 C. The resulting liquid composition was mixed with anequal weight of styrene and degassed. When 0.5% benzoyl peroxide and 2.6% toluene diisocyanate, each being based on the weightof the aforementioned varnish, wereadded tothis varnish'and the resulting mixture heated for2'-hours at-80 C. and 16 hours at l'C., an almost white, semi-translucent, tough, flexible polymer was-obtained. 'With smaller amounts of toluene diisocyanate (forexample,1.95%) softer products were obtained. With larger amounts of toluene diisocyanate (for example, 7 3.2% the products were tougher and harder. -In general, it was found that the products using toluene diis'ocyanate were similar to'thepro'ducts employing hexamethylene diisocyanate with the exception thatthe former products were more translucent, somewhat tougher, and'gelled much more rapidly. Products obtained by using hexamethylene diisocyanate to harden the stable varnish made with toluene diisocyanate a'nd'vi'ce versa had propertieswhich were practically the same as though the same diisocyana'te had been-used throughout.

EZrample 8 In this example-114 parts hydrogenated castor oil was heated with 15.5, parts toluene diiso'cyanate at 100 C. for about 1 hour. After'cooling to about 50 C. anequal amount, by Weight, oi s'tyrene'was'added to 'th'einixtu're. Then 0.5% benzo'yl peroxide and 2.7% toluene diisocyanate'were adde"d',"the latter'two ingredients being calculated on the weight of the varnish. 'ThislattertniX- 'ture'was heated for two hours at 80 C.'and'about lfi hours at 100 C. to give a solid, infusibljepinsoluble, flexible,- tough product-which wa "translucent-and -h'arder'than a similar'produot made withnon-hydrogenated castor oil. It was very tough-and retained the toughness even at100 C.

li'vhen' 67 by weight, styrene was employed insteadof 50%, by weight, used above'and otherwise-the same mixture of ingredients used, a harder resinof exceptional toughness resulted.

they still had the sanie" tt'u'ighness and -fiexibility as =tho'se re'sulting from the use of toluene diis'ocyana'te. f 1

The -styrene-diisocyanate-hyd'rogenated castor oil' products were harder and in general tougher than the-'resinsibased on-the non-hydrogenated castor oil; and had the 1 additional advantage of having better. heat resistance. Thus, a sample of the material prepared inExample8,.-when heated for about 98. hours at 150? C., turned light brown-"in color :but still retained most- 0f. its original :strength and flexibility.

. The "nature of theoross-linking reaction in the castor oil-diisocyanate-styrene system is. critical as illustrated by the following Examples 10, 11 and 12.

-Emmple-10 About 0.15%, by weight;'benzoyl'p'eroxidebased on'the'weight of the hexamethylene "diisocya'natecaster oil-styrene varnishdescribed in Example 5 "above was aded to' the latter'varnish'without further addition of 'diisocyanat'e and ther'esulting mixture heated for 20 hours at (lto give a white; sticky, visoou'sfiuid. This indicatedthat without additional amounts of 'diiso'cyanate "to cross-link the'castor'oil system; the properties of this product were quite difi'erentfrom those ordinai'ily' obtained.

. Example 11 '-Example '10 was "repeated {with 'the exception that 5%, by weight; 'pentain'ethy'l'ene"1.5 dime'thacrylate based on the weight of the varnish mixture was also added t'o'the' initial varnish. Heating of this-composition forthetime stipulated. in Example -10;.gave a cross-linked gelwhichrwas white; and fairly hard. However, this .polymer was weak and cheesy and lacking in thetoughness and rubberyness-of my castoroil-diisoc'yanate-styreneproducts.

Example-12 4 Io 10'parts' 'of the hexamethylene diisocyan'atehydrogenated castor oil-styrene varnish prepared in Example 5 was added cos umes/@0371- peroxide, 0.25 part hexamethylene diisocyanate and 0.5 part lpentamethylene 1,5 dimethaery1ate. The resultant mixture was heated for-1'7 hours at 80? C.. The resultingpolymer was harderbut less tough than a similar polymer prepared the same asabove but omitting thepentamethylene" die methacrylate. y "Examples 10, 11 and 1 2 illustrate thatthe amount of d'iisoeyanate must be su fiioient to cause 'gelation of the castor oil, that gelation of the styrenejpurtion (but not the castor oil pertionfwith'an'aotivedi-ethylenic monomer, (e. g., pentamethylene dimethacrylate) gives a distinct- 1y inferior product and that even when the amountofidiisdcyanate' is s'ufiicie'nt to cause gelation'in the castor'oilportiomthe addition of an activeidi ethylenic"monomer results in'a product which is notes tough as when the di-ethylenic monomer is omitted; V j

'As pointed out previously, my compositions tr matter have utility in casting, moldinga'nd laminating applications. -Generaly, the insoluble, infusible products obtained in accordance with my invention are soft'and rubbery and have a Shore Hardness ranging from about fi to "1007at room temperature. Even the softer, more-flexible products-do not dissolve but'm'erely swell in such strong solvent systems 'as acetone toluen'e. Because-of these properties my compositions "of matter are partieulai-lyuse'fuias potting com pounds for electrical equipment such as coils, resistors, capacitors, etc.; as solventless varnishes for the impregnation of electrical equipment; as material for use in printing rolls; as room-temperature setting adhesives for rubber, etc; in vibration damping systems, etc.

, What I claim as new and desire to secure by Letters Patent of the United States is:

1. A composition of matter comprising (1) castor oil, (2) styrene and (3) an organic diisocyanate.

2. A composition of matter comprising (1) castor oil, (2) styrene, (3) an organic diisocyanate and (4) a vinyl polymerization catalyst for the styrene.

3. A composition of matter comprising the product of reaction of a mixture of ingredients comprising (1) castor oil, (2) styrene and (3) an organic diisocyanate.

4. A composition of matter comprising (1) styrene and (2) the product of reaction of a mixture of ingredients comprising (a) castor oil and (b) an organic diisocyanate.

5. A composition of matter comprising ('1) styrene, (2) a vinyl polymerization catalyst for the styrene and (3) the product of reaction of a mixture of ingredients comprising (a) castor oil and (b) an organic diisocyanate.

6. A composition of matter comprising the product of reaction of a mixture of ingredients comprising (1) styrene, (2) a vinyl polymerization catalyst and (3) the product of reaction of a mixture of ingredients comprising (a) castor oil and (b) an organic diisocyanate.

7. A composition of matter comprising the product of reaction of a mixture of ingredients comprising (1) castor oil, (2) styrene, (3) an organic diisocyanate and (4) a vinyl polymerization catalyst for the styrene.

8. A composition of matter comprising (1) castor oil, (2) styrene and (3) toluene diisocyanate.

9. A composition of matter comprising (1) castor oil. (2) styrene and (3) hexamethylene diisocyanate.

10.A composition of matter comprising the product of reaction under heat of a mixture of ingredients comprising (1) castor oil, (2) styrene and (3) toluene diisocyanate.

11. A composition oi matter comprising the product of reaction under heat of a mixture of ingredients comprising (1) castor oil, (2) styrene and (3) hexamethylene diisocyanate.

12. A composition of matter comprising (1) styrene and (2) the product of reaction of a'mixture of ingredients comprising (a) castor oil and (b) hexamethylene diisocyanate.

13. A composition of matter comprising (1) styrene and (2) the product of reaction of a mixture of ingredients comprising (a) castor oil and (b) toluene diisocyanate.

14. A composition of matter comprising (1) styrene, (2) the product of reaction of a mixture of ingredients comprising castor oil and hexamethylene diisocyanate, (3) an organic diisocyanate and (4) a vinyl polymerization catalyst.

15. A composition of matter comprising (1) styrene, (2) the product of reaction of a mixture of ingredients comprising castor oil and toluene diisocyanate, (3) an organic diisocyanate and (4) a vinyl polymerization catalyst.

16. A composition of matter comprising the product of reaction under heat of a mixture of ingredients comprising (1) styrene, (2) the prodnot or reacting or a mixture or ingr dients c prising castor oil and hexamethylene diisocyanate, (3) anorganic diisocyanate and (4) a vinyl polymerization catalyst.

, 17. A composition of matter comprising the product of reaction under heat of a mixture of ingredients comprising (1) styrene, (2) the produce of reaction of a mixture of ingredients comcomprising (1) styrene, (2) the product of reaction of a mixture of ingredients comprising castor oil and toluene diisocyanate, (3) benzoyl peroxide and (4) toluene diisocyanate.

19. A composition of matter comprising the product of reaction of a mixture of ingredients comprising (1) styrene, (2) the product of reaction of a mixture of ingredients comprising castor oil and hexamethylene diisocyanate, (3) benzoyl peroxide and (4) hexamethylene diisocyanate.

20. A composition of matter comprising, by weight, (1) from 10 to styrene and (2) from 25 to of a mixture of castor oil and an organic diisocyanate wherein the organic diisocyanate is present in the molar ratio of from 0.1 to 2 mols of the diisocyanate per mol of the castor oil.

21. A composition of matter comprising, by weight, (1) from 10 to 75% styrene and (2) from 25 to 90% of a product of reaction obtained by heating a mixture of ingredients comprising (a) castor oil and (b) an organic diisocyanate wherein the latter is present in the molar ratio of from 0.1 to 2 mols of the organic diisocyanate per mol of the castor oil.

22. A styrene-modified composition of matter selected from a class consisting of (A a composition of matter comprising (1) castor oil, (2) styrene and (3) an organic diisocyanate and (B) a composition of matter comprising (1) styrene and (2) the product of reaction of a mixture of ingredients comprising (a) castor oil and (b) an organic diisocyanate.

23. The method which comprises (1) forming a mixture of ingredients comprising (a) castor REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Pratt et a1. Sept. 19, 1944 OTHER REFERENCES Schroeder et al.: Jour. Amer. Oil. Chem. 800., April 1949. Pp. 153-156.

Petit et al.: Ofiicial Digest, vol, 307. Auzust Number 

1. A COMPOSITION OF MATTER COMPRISING (1) CASTOR OIL, (2) STYRENE AND (3) AN ORGANIC DIISOCYANATE. 